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| United States Patent |
5,576,461
|
|
Irving
, et al.
|
November 19, 1996
|
Preparation of sulphoxonium salts
Abstract
The present invention provides a process for preparing a sulphoxonium salt
from the corresponding sulphonium salt which comprises oxidising the
sulphonium salt using a peracid, under basic conditions, in a solvent
other than a ketone.
Some of the sulphoxonium salts are new compounds.
| Inventors:
|
Irving; Edward (Higher Whitley, GB2);
Lunn; Robert J. (Bar Hill, GB2);
Taylor; David A. (Cambridge, GB2);
Haines; Alan H. (Taverham, GB2);
Innocenzi; John P. (Ashton, GB2)
|
| Assignee:
|
Ciba-Geigy Corporation (Tarrytown, NY)
|
| Appl. No.:
|
622905 |
| Filed:
|
December 6, 1990 |
Foreign Application Priority Data
| Current U.S. Class: |
568/27; 522/31; 556/69; 568/13; 568/14 |
| Intern'l Class: |
C07C 315/00 |
| Field of Search: |
522/31
568/27,13,14
556/69
|
References Cited
U.S. Patent Documents
| 4339567 | Jul., 1982 | Green | 522/31.
|
| 4398014 | Aug., 1983 | Green et al. | 522/31.
|
| 4628087 | Dec., 1986 | Meneghin | 568/27.
|
| Foreign Patent Documents |
| 1538890 | Sep., 1968 | FR.
| |
Other References
House "Modern Synthetic Reactions", Second Ed. 1972 W.A. Benjamin, Inc. pp.
321-329.
|
Primary Examiner: Chapman; Mark
Attorney, Agent or Firm: Teoli; William A., Hall; Luther A. R.
Claims
We claim:
1. A process for preparing a triaryl sulphoxonium salt from the
corresponding sulphonium salt which comprises
oxidizing the sulphonium salt using a peracid, under basic conditions, in a
solvent other than a ketone which is an alcohol, chlorinated hydrocarbon
or heterocyclic compound.
2. A process as claimed in claim 1 in which the peracid is an aliphatic or
aromatic carboxylic or sulphonic peracid.
3. A process as claimed in claim 1 in which the peracid is added as such or
is formed in situ.
4. A process as claimed in claim 1 in which the solvent is methanol,
ethanol, industrial methylated spirits, dichloromethane or
tetrahydrofuran.
5. A process as claimed in claim 1 in which the basic conditions are formed
by an alkali metal hydroxide, alkoxide, carbonate or bicarbonate.
6. A process as claimed in claim 1 which is carried out at a temperature
from below 0.degree. C. up to the reflux temperature of the reaction
mixture.
7. A process as claimed in claim 1 in which the sulphoxonium salt has the
general formula (I)
R.sup.1 R.sup.2 R.sub.3 S.sup.+ =O X.sup.- (I)
where R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is an
aryl group of 6 to 10 carbon atoms which is unsubstituted or substituted
by one or more halogen atoms, amino groups, alkyl or alkoxy groups having
1 to 8 carbon atoms, aryl groups, aryloxy groups or a group of the formula
(II) or (III)
##STR19##
where R.sup.4 is an arylene group derived from an R.sup.1 group, n is an
integer from 1 to 4, and R.sup.5 is an aryl group as defined for R.sup.1
to R.sup.3 ; and X.sup.- is an anion.
8. A process as claimed in claim 7 in which R.sup.1, R.sup.2 and R.sup.3
are selected from phenyl, tolyl, xylyl, mesityl, p-octylphenyl, biphenyl,
naphthyl, stilbenyl, p-methoxyphenyl, p-hydroxyphenyl, p-phenoxphenyl,
p-chlorophenyl, p-bromophenyl, 2,4-dimethoxyphenyl,
2,4,6-trimethoxyphenyl, m-nitrophenyl, p-dimethylaminophenyl, the group
##STR20##
and the group
##STR21##
9. A process as claimed in claim 8 in which at least one of R.sup.1,
R.sup.2 and R.sup.3 is substituted.
10. A process as claimed in claim 8 in which the formed sulphoxnium salt is
converted into another sulphoxonium salt.
11. A process as claimed in claim 10 in which a sulphoxonium salt
containing an alkoxy group is converted into one containing a hydroxy
group by reaction with hydroiodic acid at elevated temperature.
12. A process as claimed in claim 10 in which one or more nitro groups are
introduced into a sulphoxonium ion by reaction with concentrated nitric
acid.
13. A process as claimed in claim 10 in which a sulphoxonium salt with one
anion is converted into a sulphoxonium salt with a different anion by
double conversion.
14. A process as claimed in claim 7 in which anion X.sup.- is halogen,
trifluoromethanesulphonate or an ion of the formula IV
MY.sub.m.sup.- (IV)
where M is an atom of a metal or metalloid, Y is a halogen atom and m is 4,
5 or 6 and is one more than the valency of M.
15. A process as claimed in claim 14 in which anion X.sup.- is
BiCl.sub.6.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-, SbF.sub.6.sup.- or
AsF.sub.6.sup.-.
Description
The present invention relates to a process for making sulphoxonium salts
some of which are new compounds.
Sulphoxonium salts have been described as initiators for the
photopolymerisation of cationically polymerisable materials. Various
methods for their preparation have been disclosed (see for example U.S.
Pat. No. 4,339,567). One such method for triaryl sulphoxonium salts
comprises oxidation of the corresponding triarylsulphonium salt with
m-chloroperbenzoic acid in acetone solution.
We have now surprisingly found that the yield of sulphoxonium salt can be
increased and the product is not contaminated with starting material, if
the oxidation is carded out under basic conditions in a solvent other than
a ketone.
Accordingly the present invention provides a process for preparing a
triaryl sulphoxonium salt from the corresponding sulphonium salt which
comprises oxidising the sulphonium salt using a peracid, under basic
conditions, in a solvent other than a ketone.
The peracid may be added as such or formed in situ. It may be an aliphatic
peracid, but is preferably an aromatic peracid. It may be a carboxylic or
sulphonic peracid.
When generated in situ, it may be obtained by adding the carboxylic or
sulphonic acid, or a derivative thereof such as a chloride or anhydride,
together with an oxidising agent such as hydrogen peroxide, an alkali
metal peroxide or superoxide, a perborate or percarbonate.
Examples of suitable peracids include m-chloroperoxybenzoic acid,
monoperoxyphthalic acid magnesium salt, perbenzoic acid and peracids of
p-toluene sulphonic acid, benzenesulphonic acid, trichloroacetic acid and
trifluoroacetic acid.
A wide range of solvents may be used such as alcohols, e.g. methanol,
ethanol or commercial alcoholic solvents such as industrial methylated
spirits, nitriles e.g. acetonitrile, chlorinated hydrocarbons e.g.
dichloromethane and heterocyclic compounds e.g. tetrahydrofuran. The
preferred solvents are alcohols.
Basic conditions may be provided by adding a base such as an alkali metal
hydroxide, alkoxide, carbonate or bicarbonate, e.g. sodium hydroxide,
potassium carbonate, sodium methoxide, but preferably alkali metal
hydroxides or carbonates, e.g. sodium hydroxide or potassium carbonate.
The peracid may be used in sufficient quantity to carry out the oxidation,
but is preferably used in a small excess. The base is preferably present
in at least equimolar amounts compared to the amount of peracid, but
preferably a small excess is used.
The reaction may be carried out at temperatures from below 0.degree. C. up
to the reflux temperature of the reaction mixture, but ambient temperature
is preferred.
The sulphoxonium salt is preferably of the general formula (I)
R.sup.1 R.sup.2 R.sup.3 S.sup.+ .dbd.O X.sup.- (I)
where R.sup.1, R.sup.2 and R.sup.3 are the same or different and each is an
aryl group of 6 to 10 carbon atoms which is unsubstituted or substituted
by one or more halogen atoms, hydroxy groups, nitro groups, amino groups,
alkyl or alkoxy groups having 1 to 8 carbon atoms, aryl groups, aryloxy
groups, aralkenyl groups or a group of the formula (II) or (III)
##STR1##
where R.sup.4 is an arylene group derived from an R.sup.1 group, n is an
integer from 1 to 4, preferably 2, and R.sup.5 is an aryl group as defined
for R.sup.l to R.sup.3 ; and X.sup.- is an anion.
Anion X- may be a simple anion such as halogen, e.g. chloride or bromide,
trifluoromethanesulphonate or preferably an ion of the formula (IV)
MY.sub.m.sup.- (IV)
where M is an atom of a metal or metalloid, Y is a halogen atom such as
fluorine or chlorine and m is 4, 5 or 6 and is one more than the valency
of M. M may be boron, bismuth, antimony, arsenic or phosphorus. Thus anion
X.sup.- may be BiCl.sub.6.sup.-, BF.sub.4.sup.-, PF.sub.6.sup.-,
SbF.sub.6.sup.- or AsF.sub.6.sup.-.
Examples of aryl groups R.sup.1, R.sup.2 or R.sup.3 include phenyl, tolyl,
xylyl, mesityl, p-octylphenyl, biphenyl, naphthyl, stilbenyl,
p-methoxyphenyl, p-hydroxyphenyl, p-phenoxyphenyl, p-chlorophenyl,
p-bromophenyl, 2,4-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, m-nitrophenyl,
p-dimethylaminophenyl, the group
##STR2##
and the group
##STR3##
Preferably at least one of R.sup.1, R.sup.2 and R.sup.3 is substituted.
Some of the sulphoxonium compounds of formula (I) are new and form another
aspect of the present invention. The new compounds are those of formula
(I) where at least one of R.sup.1, R.sup.2 and R.sup.3 is substituted by
hydroxy, amino, nitro, aryl, aryloxy, aralkenyl or a group of the formula
II or III.
It should be noted that sulphoxonium salts with one anion can be easily
converted into salts with a different anion by double conversion. For
example a hexafluorophosphate can be made by reacting the corresponding
sulphoxonium chloride with potassium hexafluorophosphate. In a similar way
the starting sulphonium salt can also be made with a desired anion.
It is also possible to carry out reactions to introduce or change
substitutents on an aryl ring in the sulphoxonium cation. For example
ether cleavage of an alkoxy group will produce a hydroxy group
substituent. This may be carded out for instance using hydriodic acid at
elevated temperature. Nitro groups may be introduced by a nitration
reaction using concentrated, preferably fuming nitric acid.
The sulphonium salts used as starting materials are either known or can be
made by methods known per se e.g. as described by Crivello and Lam, J.
Polymer Sci., Polymer Chemistry: 1980, 18, 2697-2714; or by Endo, Shudo
and Okamoto, Chem. Pharm. Bull: 1981, 29, (12), 3753-3755.
The sulphoxonium salts obtained according to the present invention are
useful as cationic photoinitiators for cationically polymerisable
materials. They may be used in amounts of 0.1 to 7.5, preferably 0.5 to
5.0 parts by weight per 100 parts by weight of polymerisable material.
The sulphoxonium salts may be used alone or together with a sensitiser to
increase the speed of curing. Suitable sensitisers include dyes or
aromatic polycyclic compounds such as anthracene, 9-methylanthracene,
rubrene, perylene, acenaphthene, phenanthrene, fluoroanthene and pyrene.
Other suitable sensitisers are disclosed in U.S. Pat. No. 4,069,054.
A wide range of cationically polymerisable materials may be
photopolymerised using sulphoxonium salts obtained by the present
invention e.g. those described in U.S. Pat. No. 4,339,567 including
epoxides, vinyl compounds, aminoplasts and phenoplasts. Preferred
compounds are aromatic glycidyl ethers, especially aromatic diglycidyl
ethers.
The invention is illustrated by the following Examples.
In the Examples, IR spectra were obtained using a KBr disc for solid
products and a liquid film for liquids; nmr data were obtained using a
machine with a spectral frequency of 250 MHz and using d.sub.6 acetone.
EXAMPLE 1
Triphenylsulphonium hexafluorophosphate (75 g, 177 mmole) is suspended in
methanol (1250 ml) and potassium carbonate (152 g, 1.1 mole) is added. The
stirred suspension is cooled to 0.degree. C. and m-chloroperoxybenzoic
acid (159 g, 0.92 mole) is added. The suspension is stirred at 0.degree.
C. for 7 hours and then at room temperature for 3 days. 1M aqueous sodium
thiosulphate solution (920 ml) is added to reduce the oxidizing species.
The methanol is removed under reduced pressure and a white precipitate
forms. This is collected, washed with water and diethyl ether and dried in
vacuo at 50.degree. C. Yield 61.2 g, 79%, mp 260.degree.-261.degree. C.
IR: 1455, 1225, 1080, 840, 755,730, 680 cm.sup.-1 : 8.04 (m,6H), 8.16 (m,
9H) ppm
EXAMPLES 2 to 12
Following the procedure of Example 1 using the appropriate sulphonium salt,
the following sulphoxonium salts are prepared.
__________________________________________________________________________
Example
Salt Yield (%)
m.p. (.degree.C.)
__________________________________________________________________________
##STR4## 95 oil
IR: 1580, 1440, 1305, 1150, 1080, 840, 730 cm.sup.-1
.delta.:
7.09(t, J=9Hz), 7.44-7.70(m), 7.90-8.20(m)ppm
3
##STR5## 57 121-123
IR: 1575, 1440, 1305, 1150, 1075, 840, 725, 680 cm.sup.-1
.delta.:
7.52-8.74(m)ppm
4
##STR6## 75 170-172
IR: 1600, 1440, 1230, 1090, 850, 740, 710, 680 cm.sup.-1
.delta.:
2.60(s, 3H), 7.81(d, J=9Hz, 2H), 8.00(m, 6H), 8.16(m, 6H)ppm
5
##STR7## 40 81-83
IR: 1590, 1450, 1315, 1090, 840, 765, 735, 690 cm.sup.-1
.delta.:
7.64(m, 6H), 7.90-8.20(m, 8H), ppm
6
##STR8## 90 oil
IR: 1580, 1440, 1080, 840, 750, 725, 695, 670 cm.sup.-1
.delta.:
7.35-8.25(m, 19H), ppm
7
##STR9## 68 157-159
IR: 1600, 1290, 1090, 850, 715, cm.sup.-1
.delta.:
4.05(s, 3H), 7.46(d, J=9Hz, 2H), 7.95-8.20(m, 14H), ppm
8
##STR10## 58 216-218
IR: 1600, 1455, 1385, 1210, 1090, 850, 760, 740, 710, 690, 645,
cm.sup.-1
.delta.:
3.24(s, 6H), 7.08(d, J=9Hz, 2H), 7.63(d, J=9Hz, 2H), 7.97(m, 4H),
8.10
(m, 6H), ppm
9
##STR11## 80 oil
IR: 1580, 1260, 1080, 840, 750, 725, 705, 675, cm.sup.-1
.delta.:
6.80-8.20(m, 19H), ppm
10
##STR12## 90 semi-solid
IR: 1580, 1080, 840, 690, 660, cm.sup.-1
.delta.:
2.58(s, 9H), 7.81(m, 6H), 7.96(m, 6H)ppm
11
##STR13## 40 oil
IR: 1580, 1440, 1080, 840, 720, 670, cm.sup.-1
.delta.:
7.50-8.20(m, 14H)ppm
12
##STR14## 73 semi-solid
IR: 1590, 1450, 1080, 840, 755, 730, 710, 680, 635, cm.sup.-1
.delta.:
3.00(br, 4H), 7.83(d, J=9Hz, 4H), 8.00(12H, m), 8.14(12H, m)ppm
13
##STR15## 60 213-4
IR: 1450, 1270, 1225, 1160, 1080, 1035, 770, 685, 640 cm.sup.-1
.delta.:
8.00(m, 6H), 8.20(m, 9H)ppm
__________________________________________________________________________
EXAMPLE 14
Triphenylsulphonium hexafluorophosphate (0.5 g, 1.23 mmole) is dissolved in
methanol (40 ml) and cooled to 0.degree. C. Potassium carbonate (2.15 g,
15.6 mmole) is added followed by monoperoxyphthalic acid magnesium salt
(1.52 g, 3.08 mmole). The suspension is stirred at 0.degree. C. for 7
hours and then at room temperature for 2 days during which time the
suspension thickens and stirring is ceased. 2M aqueous hydrochloric acid
is added to take the pH of the suspension to 5 followed by 1M aqueous
sodium thiosulphate until no oxidizing species are present. The methanol
is removed under reduced pressure and the white precipitate is collected,
washed with water and diethyl ether and finally dried in vacuo at
50.degree. C. Yield 0.25 g, 48%, m.p. 259.degree.-260.degree. C.
EXAMPLES 15 to 17
Following the procedure of Example 14 using the appropriate sulphonium
salt, the following sulphoxonium salts are prepared.
__________________________________________________________________________
Example
Salt Yield (%)
m.p. (.degree.C.)
__________________________________________________________________________
15
##STR16## 46 wax
IR: 1585, 1080, 840, 750, 730, 680 cm.sup.-1
.delta.:
0.85(m, 2H), 1.23(m, 10H), 1.66(m, 1H), 2.85(m, 4H), 7.40-8.20
(m, 14H)ppm
16
##STR17## 51 155-157
IR: 1230, 1085, 850, 760, 730, 705 cm.sup.-1
.delta.:
2.61(s, 3H), 7.82(d, J=9Hz, 2H), 8.02(m, 6H), 8.18(m, 6H)ppm
17
##STR18## 61 131-133
IR: 1585, 1450, 1220, 1080, 1050, 760, 730, 705, 680 cm.sup.-1
.delta.:
2.60(s, 3H), 7.81(d, J=9Hz, 2H), 8.00(m, 6H), 8.15(m,
__________________________________________________________________________
6H)ppm
EXAMPLE 18
Triphenylsulphonium hexafluorophosphate (0.5 g, 1.23 mmol) is dissolved
with stirring at room temperature in ethanol (20 ml). 10 ml of a solution
of saturated potassium carbonate solution are added, and the two-phase
mixture stirred whilst solid monoperoxyphthalic acid magnesium salt
hydrate (1.52 g, 3.08 mmol) is added. The mixture is stirred for 5 hours
before working up as in Example 1 to given an off-white powder (0.24 g,
46%) m.p. 256.degree.-257.degree. C.
EXAMPLE 19
Triphenylsulphonium hexafluorophosphate (0.5 g, 1.23 mmol) is dissolved in
methanol (20 ml) and potassium carbonate (2.15 g, 15.6 mmol) is added. The
resulting suspension is stirred at room temperature while a solution of
monoperoxyphthalic acid magnesium salt hydrate (1.52 g, 3.08 mmol) in
methanol (10 ml) is added dropwise over 2 hours.
After a total of 5 hours the reaction is worked up as in Example 14 to give
a white solid 0.41 g, 79% with m.p. 258.degree.-260.degree. C.
EXAMPLE 20
Example 14 is repeated but at room temperature and after 5 hours the
reaction is worked up to give product 0.3 g (58%) with m.p.
258.degree.-260.degree. C.
EXAMPLE 21
Example 14 is repeated but at 8.degree.-9.degree. C. and after 5 hours the
reaction is worked up to give product 0.28 g (54%) with m.p.
259.degree.-261.degree. C.
EXAMPLE 22
Example 14 is repeated but using industrial methylated spirits solvent (20
ml); giving product 0.31 g (60%) with m.p. 256.degree.-258.degree. C.
EXAMPLE 23
Triphenylsulphonium hexafluorophosphate (2.5 g, 6.15 mmol) is dissolved in
industrial methylated spirits (50 ml) and stirred at room temperature with
saturated potassium carbonate solution (30 ml) in a two-phase system. A
solution of monoperoxyphthalic acid magnesium salt hydrate (7.6 g, 15.4
mmol) is added dropwise over one and half hours. After a total of 5 hours
the reaction mixture is filtered. The solid collected is washed with
dilute hydrochloric acid, water and ether to give 1.36 g of a white solid
m.p. 263.degree.-4.degree. C. The filtrate is worked up as in Example 1 to
give a white solid 0.17 g m.p. 263.degree.-264.degree. C. Combined yield
59%.
EXAMPLE 24
Triphenylsulphonium hexafluorophosphate (10.5 g, 0.026 mmol) and
p-toluenesulphonyl chloride (29.4 g, 0.15 mol) are dissolved in methanol
(310 ml) with stirring at room temperature. A solution of hydrogen
peroxide (30%, 32 ml, 0.28 mol) and sodium hydroxide (24.7 g, 0.62 mol) in
water (210 ml) is added slowly over 45 min causing an exotherm to ca.
45.degree. C.
After one hour, methanol is distilled off under reduced pressure and the
resulting precipitate is washed with water and ether to give
triphenylsulphoxonium hexafluorophosphate (10.38 g, 95%) as a beige solid
with spectra identical to those of authentic material.
EXAMPLE 25
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) is
dissolved with stirring in methanol (40 ml). The resulting solution is
cooled in an icewater bath while solid potassium superoxide (2.20 g, 31
mmol) is added slowly (with evolution of oxygen). After stirring for a
further 15 minutes, a solution of p-toluenesulphonyl chloride (2.38 g,
12.5 mmol) in 30 ml methanol is added dropwise over 20-30 minutes. The
reaction mixture is stirred for a further 30 min. After this time the
mixture is filtered under vacuum. The residue is washed with methanol and
the combined filtrate evaporated under reduced pressure. The resulting
solid is slurried with water, filtered, and washed with water and ether,
to give (tolyl)diphenylsulphoxonium hexafluorophosphate (0.6 g, 54 %)
identical with authentic material.
EXAMPLE 26
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) is
dissolved with stirring in methanol (40 ml). The reaction mixture is
cooled in an ice-water bath while sodium peroxide (2.42 g, 31 mmol) is
added slowly. After 15 minutes, p-toluenesulphonyl chloride (2.38 g, 12.5
mmol) in 30 ml methanol is added dropwise over 20 minutes. After a further
1 hour the mixture is filtered under vacuum. The residue is washed with
methanol and the combined filtrate evaporated in vacuo. Water is added and
the product collected by filtration and washed with water and then ether.
The resultant (tolyl)diphenylsulphoxonium hexafluorophosphate (0.35 g,
31%) was identical with authentic material.
EXAMPLE 27
A reaction exactly as in Example 26, but carded out in industrial
methylated spirits instead of methanol gives the sulphoxonium salt (1.11
g, 99%).
EXAMPLE 28
Benzenesulphonyl chloride (2.20 g, 0.0125 mol) in methanol (30 ml) is added
dropwise over 20 minutes to an ice-cooled mixture of potassium superoxide
(2.20 g, 0.031 mol), triphenylsulphonium hexafluorophosphate (1.05 g,
0.00257 mol) and methanol (40 ml). After 30 minutes the mixture is
filtered and the filtrate evaporated in vacuo to ca. 5 ml, affording a
white precipitate. This is collected and washed with water to give a solid
(0.735 g). A further 0.2 g is obtained by trituration of the residue from
filtration in dichloromethane, filtering, and concentration in vacuo.
Total yield of triphenylsulphoxonium hexafluorophosphate is 0.935 g (86%).
EXAMPLE 29
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mol) is
dissolved in methanol (40 ml) with cooling in an ice-water bath. Sodium
peroxide (2.42 g, 31 mmol) is added slowly. After 15 mins a solution of
trichloro- acetyl chloride (1.4 ml, 12.5 mol) in methanol (30 ml) is added
over 20 mins. After a further 30 mins the reaction mixture is filtered
under vacuum and the filtrate evaporated in vacuo. Water is added and the
resulting solid collected, washed with water and ether to give
(tolyl)diphenylsulphoxonium hexafluorophosphate (0.72 g, 64% ) with
spectra identical to those of authentic material.
EXAMPLE 30
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mol) and
p-toluenesulphonyl chloride (2.38 g, 12.5 mmol) are dissolved with
stirring in methanol (40 ml) with cooling in ice water. Sodium methoxide
(1.67 g, 31 mmol) and hydrogen peroxide (30% in water, 3.5 g, 31 mmol) are
added over 25 mins. After 1 hour the reaction mixture is filtered and
evaporated in vacuo. Water is added and the resulting solid is collected
and washed with water and ether to give (tolyl)diphenylsulphoxonium
hexafluorophosphate (1.08 g, 96% ) with spectra identical to those of
authentic material.
EXAMPLE 31
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mol) is
dissolved with stirring in methanol (40 ml) with cooling in an ice-water
bath. Sodium methoxide (2.42 g, 31 mmol) is added slowly. After 15 mins a
solution of trifluoroacetic anhydride (1.8 ml, 12.5 mmol) in methanol (30
ml) is added dropwise over 25 min. After 30 min the reaction mixture is
filtered and evaporated under reduced pressure. Water is added and the
resulting solid is collected and washed with water and ether, to give
(tolyl)diphenylsulphoxonium hexafluorophosphate (0.85 g, 76%) identical to
authentic material.
EXAMPLE 32
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mol) is
dissolved with stirring in methanol (40 ml) with cooling in ice-water.
p-Toluenesulphonyl chloride (2.38 g, 12.5 mmol) is added slowly. After 15
mins a solution of hydrogen peroxide (30% in water, 3.5 g, 31 mmol) and
sodium hydroxide (1.24 g, 31 mmol) in water (25 ml) is added dropwise over
10 min. After a further one and a half hours the reaction mixture is
filtered and evaporated in vacuo. Water is added and the resulting solid
is collected and washed with water and ether, to give
(tolyl)diphenylsulphoxonium hexafluorophosphate (0.88 g, 79%) identical to
authentic material.
EXAMPLE 33
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mol) and sodium
methoxide (1.67 g, 31 mmol) are dissolved with stirring in methanol (40
ml). The resulting solution is cooled in an ice-water bath while
urea-hydrogen peroxide complex (1:1, 2.91 g, 31 mmol) is added slowly.
After 15 mins a solution of p-toluenesulphonyl chloride (2.38 g, 12.5
mmol) in methanol (30 ml) is added dropwise over 20 min. After a futher 1
hour the reaction mixture is filtered and evaporated under reduced
pressure. Water is added and the resulting solid collected, and washed
with water and ether. The resultant (tolyl)diphenylsulphoxonium
hexafluorophosphate (0.53 g, 47%) is identical to authentic material.
EXAMPLE 34
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) and
p-toluenesulphonyl chloride (2.38 g, 12.5 mmol) are dissolved with
stirring in methanol (40 ml). The resulting solution is stirred in an
ice-water bath while a solution of sodium percarbonate (4.87 g, 31 mmol)
in water (30 ml) is added over 15 min. After 30 min the reaction mixture
is filtered and evaporated under reduced pressure. Water is added and the
resulting solid collected, and washed with water and ether. The resulting
slightly damp (tolyl)diphenylsulphoxonium hexafluorophosphate (1.21 g) is
identical to authentic material.
EXAMPLE 35
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) and
p-toluenesulphonyl chloride 2.38 g, 12.5 mmol are dissolved in methanol
(40 ml) with stirring in an ice-water bath. A solution of sodium carbonate
(3.29 g, 31 mmol) and hydrogen peroxide (30% in water, 3.5 g, 31 mmol) in
water (30 ml) is added dropwise over 20 mins. After a further 30 min the
reaction mixture is filtered and evaporated in vacuo. Water is added and
the resulting solid collected and washed with water and ether. The
resultant (tolyl)diphenyl- sulphoxonium hexafluorophosphate (1.06 g, 95%)
is identical to authentic material.
EXAMPLE 36
(p-Methoxyphenyl)diphenylsulphonium hexafluoro- phosphate (5.6 g, 12.8
mmol) and p-toluenesulphonyl chloride (6.1 g, 32 mmol) are dissolved in
methanol (300 ml) with stirring at 15.degree. C.
A solution of sodium hydroxide (5.1 g, 0.31 mmol) and hydrogen peroxide
(30% in water, 6.7 g, 60 mmol) in water (50 ml) is added dropwise. The
reaction mixture is stirred, and allowed to reach room temperature
overnight. Methanol is removed in vacuo to give a white granular solid.
After collection and washing with water and ether
(p-methoxyphenyl)diphenyl- sulphoxonium hexafluorophosphate (4.9 g, 84%)
is obtained identical to authentic material.
EXAMPLE 37
Triphenylsulphonium hexafluoro-phosphate (1.05 g, 2.57 mmol) and
p-toluenesulphonyl chloride (0.73 g, 3.9 mmol) are dissolved with stirring
in methanol (35 ml) at room temperature. A solution of sodium peroxide
(0.5 g, 6.4 mmol) in water (30 ml) is added dropwise over 30 min. After 2
hours water is added and the white solid collected, washed with water and
ether. The resulting triphenylsulphoxonium hexafluorophosphate (0.56 g,
52%) is identical to authentic material.
EXAMPLE 38
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) and
p-toluenesulphonyl chloride 2.38 g, 12.5 mmol are dissolved with stirring
in tetrahydrofuran (40 ml). A solution of sodium peroxide (2.42 g, 31
mmol) in water (30 ml) is added dropwise over 25 minutes. After a further
hour the reaction mixture is filtered and evaporated under reduced
pressure. Water is added and the resulting solid collected, and washed
with water and ether. The resulting white solid (1.06 g, 95% ) has spectra
identical to those of authentic material.
EXAMPLE 39
Triphenylsulphoxonium hexafluorophosphate (1 g, 2.36 mmol) is dissolved in
concentrated H.sub.2 SO.sub.4 (10 ml) and is kept at 15.degree. C. in a
water bath. Then fuming nitric acid (1.1 equiv. 0.18 g, 0.12 ml) is added.
The stirred solution is heated at 80.degree.-90.degree. C. for 6 hours. It
is allowed to cool and is poured into aqueous potassium
hexafluorophosphate solution. The yellow precipitate is collected and
washed with water until the washings are neutral. The filter cake is then
washed with diethyl ether and dried in vacuo at 40.degree. C. Yield of the
mononitrated product is 1 g, 91%, m.p. 93.degree.-96.degree. C.
IR: 1530, 1350, 1225, 1075, 840, 725 cm.sup.-1 : 8.00-9.00 (m,14H) ppm
EXAMPLE 40
(4-Methoxyphenyl)diphenylsulphoxonium hexafluoro- phosphate (3 g, 6.6 mmol)
is stirred at 120.degree.-125.degree. C. in hydriodic acid (57% in water,
15 ml) for 4 hours. It is allowed to cool and is poured into potassium
hexafluorophosphate solution. The precipitate is collected and found to be
(4-hydroxyphenyl)diphenylsulphoxonium hexafluorophosphate, yield 20% m.p.
200.degree.-202.degree. C.
IR: 3200, 1580, 1080, 840, 755,730, 710, 680 cm.sup.-1 : 7.35 (d,J=9
Hz,2H), 7.98 (m,6H), 8.16 (m,6H), 10.75 (br,1H) ppm
EXAMPLE 41
Example 39 is repeated but using 5 equivalents of nitric acid. The yield of
tris(m-nitrophenyl)sulphoxonium hexafluorophosphate is 74%, m.p.
135.degree.-139.degree. C.
IR: 1600, 1540, 1355, 845,730, 660 cm.sup.-1 : 8.00-9.20 (m,12H) ppm
EXAMPLE 42
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) is
dissolved with stirring in acetonitrile (40 ml). The resulting solution is
stirred while p-toluene- sulphonyl chloride (2.38 g, 12.5 mmol) added. The
reaction mixture is cooled in an ice-water bath. A solution of sodium
peroxide (2.42 g, 31 mmol) in water (30 ml) is added dropwise over 20
minutes. After a further 2 hours the reaction mixture is filtered under
vacuum and the filtrate evaporated in vacuo. Water is added and the
resulting solid collected, and washed with water and ether to give
(tolyl)diphenylsulphoxonium hexafluorophosphate (0.63 g, 56%) with spectra
identical to authentic material.
EXAMPLE 43
(Tolyl)diphenylsulphonium hexafluorophosphate (1.08 g, 2.57 mmol) and
p-toluenesulphonyl chloride (2.38 g, 12.5 mmol) are dissolved with
stirring in dichloromethane (40 ml), with cooling in ice-water. A solution
of sodium peroxide (2.42 g, 31 mmol) in water (30 ml) is added dropwise
over 20 minutes. After further stirring overnight the reaction mixture is
diluted with dichloromethane and water. The mixture is allowed to separate
and the dichloromethane containing layer collected, dried over magnesium
sulphate, filtered and evaporated in vacuo. The resulting solid is
slurried in water and collected. It is further washed with water and ether
to yield (tolyl)diphenylsulphoxonium hexafluorophosphate (0.73 g, 65%)
identical to authentic material.
EXAMPLES 44-48
Compositions comprising 2,2-bis(p-glycidyloxyphenyl)propane (100 parts by
weight) a sulphoxonium salt as indicated in the Table below (3 parts by
weight) with and without 1 part by weight of 9-methyl- anthracene as
sensitiser, are applied as a film 24 .mu.m thick on tinplate. They are
then exposed in two ways to produce a tack free coating. The first is
simple exposure to a metal halide lamp (5000 w) at a distance of 75 cm and
the time taken to become tack-free is recorded. The second is to expose
the film to radiation from a medium pressure mercury arc lamp (80 W per
cm) at a distance of 8 cm on a Primarc type apparatus running at 21.3
m/min. The number of passes needed for a tack-free coating is recorded.
______________________________________
Time No. of Passes
Salt from with with
Example
Example sensitiser sensitiser
______________________________________
44 2 7.5 min 15 sec 6 5
45 6 1 min 8 sec 3 2
46 9 3.3 min 15 sec 5 4
47 12 4.25 min 25 sec 9 5
48 36 2 min 6 sec 3 2
49 38 2.5 min 6 sec 2/3 2
______________________________________
EXAMPLES 50-55
The procedure of Examples 44-49 is repeated using, as the resin,
3,4-epoxycyclohexylmethyl 3',4'-epoxy cyclohexane carboxylate. The
following results are obtained.
______________________________________
Time No. of Passes
Salt from with with
Example
Example sensitiser sensitiser
______________________________________
50 2 >10 min 40 sec 2/3 1/2
51 6 3.5 min 12 sec 2/3 1/2
52 9 10 min 13 sec 2/3 2
53 12 >10 min 45 sec 3/4 2/3
54 36 >10 min 14 sec 3 2
55 38 >10 min 7 sec 2/3 2
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